| Abstract: | The solubility products of CaO and MgO in liquid iron, measured using the emf oxygen sensor, are several orders of magnitude greater than those calculated from the thermochemical data. This would imply that the values of Δ and Δ derived from the solubility products are, by a large amount, less negative than those given in the compiled thermochemical tables. As is shown in this paper, the values of Δ derived indirectly from numerous experimental data on various gas-solid (-liquid) reactions involving pure CaO, are in general accord with the compiled thermochemical data. It is surmised from these observations that the oxygen activities in liquid iron saturated with CaO or MgO, measured by the emf cell, giving high solubility products of CaO and MgO, may be attributed to the failure of the emf oxygen sensor in liquid iron containing dissolved calcium or magnesium. Two reaction mechanisms are discussed in the paper to account for the malfunction of the oxygen sensor under highly reducing conditions, which will prevail in liquid iron containing even a small amount of dissolved calcium or magnesium. These two mechanisms are (i) redox reaction at the (Y2O3)ThO2 electrolyte/melt interface and (ii) oxygen flux through the electrolyte from the reference electrode Cr–Cr2O3 to the melt/electrolyte interface. Suggestions are made for some experimental work to confirm or refute the argument presented in this communication. |
